Dispersible anthraquinone dyestuffs

ABSTRACT

DIFFICULTY WATER-SOLUBLE ANTHRAQUINONE DYESTUFFS FREE FROM WATER-SOLUBILIZING GROUPS WHICH DISSOCIATE ACID IN WATER BEARING IN AT LEAST ONE B-POSITION, EITHER DIRECTLY OR BY WAY OF A BRIDGING MEMBER, THE GROUPING -Y-O-COOR, WHEREIN Y REPRESENTS AN ALKYLENE GROUP, OPTIONALLY SUBSTITUTED BY A HYDROXYL GROUP AND R REPRESENTS AN OPTIONALLY SUBSTITUTED ALIPHATIC, CYCLOALIPHATIC OR AROMATIC RADICAL; THESE DYESTUFFS BEING SUITED PARTICULARLY FOR THE DYEING OF OF SYNTHETIC ORGANIC FIBERS, ESPECIALLY POLYETHYLENE GLYCOL TEREPHTHALATE FIBERS, AFFORDING DYEEINGS ON THESE FIBERS WHICH HAVE GOOD FASTNESS PROPERTIES AND ESPECIALLY GOOD FASTNESS TO LIGHT AND SUBLIMATION.

United States Patent 3,803,168 DISPERSIBLE ANTHRAQUINONE DYESTUFFS Hans-Peter Kolliker, Muenchenstein, Alfred Staub, Binningen, and Peter Hindermann, Bottmingen, Switzerland, assignors to Ciba-Geigy AG, Basel, Switzerland No Drawing. Continuation-impart of application Ser. No. 24,810, Apr. 1, 1970, now Patent No. 3,689,510. This application Jan. 21, 1972, Ser. No. 219,853 Claims priority, application Szvtzerland, Apr. 2, 1969,

Int. or: com 27/52 US. Cl. 260-326 C 4 Claims ABSTRACT OF THE DISCLOSURE This is a continuation-in-part application of US. application, Ser. 24,810, filed Apr. 1, 1970, now US. Pat. No. 3,689,510.

The present invention relates to sparingly water-soluble anthraquinone dyestuffs, usable as dispersion dyestufls, to processes for their production, to the use of these anthraquinone dyestuffs for the dyeing or printing of synthetic organic textile fibres, especially textile fibres made from linear polyesters of aromatic polycarboxylic acid with polyfunctional alcohols, or made from cellulose esters and, the textile fibres dyed or printed with said dyestufis.

It has been found that difiiculty water-soluble anthraquinone dyestuifs being free from water-solubilizing groups dissociating acid in water and corresponding to the Formula I,

are characterized by particularly advantageous properties e.g. good aflinity on polyester fibres combined with good fastness to light and sublimation of the dyeings produced therewith.

In the above Formula I A represents the radical of an anthraquinone dyestuif which is linked with Y, in at least one B-position, either directly or by way of a bridging member,

Y represents an alkylene group, optionally substituted by a hydroxyl group, and

R represents an optionally substituted aliphatic, cycloaliphatic or aromatic radical.

The anthraquinone dyestuffs of Formula I are obtained by condensing an anthraquinone compound of the Formula II,

wherein A and Y have the meaning given under Formula I, with a halogeno formic acid ester of the Formula III,

Hal-COOR (HI) wherein Hal represents chlorine or bromine and R has the meaning given under Formula I.

The starting materials are so chosen that the obtained anthraquinone dyestuif contain no water-solubilizing groups dissociating acid in water, i.e. it contains, e.g. no sulphonic acid groups, carboxylic acid groups or phosphoric acid groups.

The anthraquinone compounds, usable as starting materials and containing, in at least one fl-position, a hydroxyalkyl radical bound either directly or by way of a bridging member to the anthraquinone neucleus, can belong to the series of the actual anthraquinonyl compounds as well as to that of the higher condensed derivatives, e.g. to the group of the anthraquinonyl or anthrapyrimidinyl compounds.

The anthraquinone nucleus can contain, in addition to the substituents -YO-COOR in B-position, further substituents, e.g. primary amino groups or secondary amino groups which can be substituted by a lower alkyl group such as the methyl, isopropyl or sek. butyl group, a cycloalkyl group such as the cyclohexyl group, a monoor polynuclear aryl group, e.g. phenyl, chlorophenyl, methylphenyl such as the toluyl or 2,4,6-trimethylphenyl group, methox'yphenyl, phenoxyphenyl or phenylazophenyl group as well as hydroxy, cyano or nitro groups, or halogens such as fluorine, chlorine or bromine.

The anthraquinone radical A can be bound direct to Y or by way of a bivalent or trivalent bridging member. Bivalent bridging members can be double-bonding atoms such as oxygen or sulphur, or double-bonding groups. Suitable double-bonding groups are, e.g. those containing heteroatoms, e.g. a COO--, CO-NH-,

group (whereby R denotes hydrogen or a lower alkyl radical, the alkylene group has at most 4 carbon atoms and the phenylene group may be substituted by halogen such as chlorine, or lower alkyl groups). Suitable as triavlent bridging member is, in particular, the o-dicarboxylic acid imide group.

The alkylene group Y contains 1-6 carbon atoms and preferably at most 4 carbon atoms and can be straightchained or branched; in the former case it is preferably the 1,2-ethylene or 1,3-propylene group, in the latter case it is the 2-rnethyl-l,3-propylene or 2,2-dimethyl-1,3-propylene group. If the alkylene group Y is substituted by a hydroxyl group, it represents especially a 2-hydroXyl-1,3- propylene group.

If R represents an aliphatic radical, then it is, e.g. a straight or branch-chained, optionally substituted alkyl or alkenyl group (in the latter case especially a A alkenyl group) having preferably up to 5 carbon atoms. As substituents, these aliphatic radicals, especially the alkyl group, can contain, e.g. halogens such as chlorine or bromine, or a lower alkoxy group as well as a carbocyclic ring having, in particular, aromatic character such as the phenyl radical, or heterocyclic rings such as the thieny1-(2)-, furyl-(2)- or tetrahydrofuryl-(2)- radical.

Cycloaliphatic radicals denoted by R are, e.g. cycloalkyl groups having preferably or 6-membered rings and especially the cyclohexyl or methylcyclohexyl group.

When R represents an aromatic radical, then this radical preferably belongs to the benzene series; it can contain usual non-ionogenic ring substituents. Such substituents are, e.g. halogens such as fluorine, chlorine or bromine, C -C -alkoxy or lower C C -alkyl groups, preferably chlorine or methyl groups.

Starting materials of the Formula II are for the most part known or they can be produced by methods known per se.

Anthraquinone compounds of the Formula II, in which the radical A is bound to Y by way of oxygen, sulphur, an -Oalkylene-O-,

-Oalkylenecycloalkylene-alkylene-O-group,

can be obtained, e.g. using the process of the German Pat. 1,209,680 or of the British Pat. 974,404, e.g. by reacting an anthraquinone compound of the Formula 1V,

AW (IV) wherein A represents a B-anthraquinonyl radical, and W represents halogen, the sulphonic acid group or a phenoxy group,

with a compound of the Formula V,

wherein Y has the meaning given under Formula I,

X represents oxygen or sulphur, and

Q represents the direct bond or a bivalent hydrocarbon radical optionally interrupted by oxygen.

Examples of anthraquinone compounds of the Formula IV are:

1-amino-2-bromoanthraquinone, l,4-diamino-2-bromoanthraquinone, 1-amino-4-hydroxy-2-bromo or -2-chloroanthraq1uinone, 1-amino-4-hydroxy-Z-phenoxy-anthraquinone, 1-amino-4-hydroxyanthraquinone-Z-sulphonic acid, 1-amino-4-phenylaminoanthraquinone-2-sulphonic acid, 1-amino-4-cyclohexylaminoanthraquinone-2-sulphonic acid, 1-amino-4-hydroxy-2-p-methoxyphenoxy-anthraquinone.

Examples of compounds of the Formula V are: glycols such as ethyleneglycol, 1,3-propyleneglycol, 2,2-diethylpropanediol- 1,3 cyclohexanedimethanol, cyclohexanediethanol, cyclohexane-di-n-butanol, 2,5 bis-(fi-hydroxymethyl) tetrahydrofuran, 2,5 bis (B-hydroxyethyD- tetrahydrofuran, di-(fl-hydroxyethoxy)-benzene, also mor p-(,8hydroxycthoxy)-phenol, ,B-(p-hydroxy-phenyletb yl alcohol, m-hydroxybenzyl alcohol, mercaptoalkyl alcohols such as Z-mercapto-ethanol, 3-mercapto-1-propa- 1101 or 4-mercapto-l-butanol.

Starting materials of the Formula II, in which Y is bound to A by way of a --SO NH or CONH- group or by way of a O-phenyleneSO NH, OphenyleneCONH, -SphenyleneSO NH- or SphenyleneCONH group, can be obtained by reacting a halide of the Formula VI,

A'Q'X Hal (VI) wherein A represents a fl-anthraquinonyl radical,

Q represents the direct bond or a phenylene group which is linked to A by way of'oxygen or sulphur,

X; represents the -CO- or SO bond, and

Hal represents chlorine Qt bIQIQiI with an amine of the Formula VII,

NH Y--OH (VII) wherein Y has the meaning given under Formula I.

Halides of the Formula VI are, e.g.

1-aminoanthraquinone-Z-carbonyl chloride,

l-amino-4-phenylaminoanthraquinone-2-carbonyl chloride,

l-amino-4-hydroxy-anthraquinone-2-phenoxy-3-carbonyl chloride,

1-amino-4-hydroxy-anthraquinone-2-phenoxy-4'- sulfonylchloride, or

1-amino-4-hydroxy-anthraquinone-2-phenylthio-4'- sulfonyl chloride,

and amines of the Formula VII are, e.g. ethanolamine or 1,3-propanolamine.

The production of the anthraquinone compounds of the Formula II, wherein A represents a methyl group, which is bound to the anthraquinone nucleus A direct or by Way of a phenoxy group, is described, e.g. in the French Pat. No. 1,530,985.

Examples of such starting materials of the Formula II are:

l,4-diamino-2-hydroxymethyl-anthraquinone,

1,4-dihydroxy-Z-hydroxymethyl-anthraquinone,

1-amino-2-hydroxymethyl-4-phenylamino-anthraquinone,

and

1-hydroxy-2-hydroxymethyl-4-phenylaminoanthraquinone.

The halogeno formic acid esters of the Formula III, usable as starting materials, are likewise for the most part known.

Such esters are: halogeno formic acid-alkyl, -alkenyl, -cycloalkyl or -aryl esters, e.g. chloroformic acid methyl ester, chloroformic acid ethyl ester, chloroformic acid isopropyl ester, chloroformic acid amyl ester, chloroformic acid allyl ester, chloroformic acid cyclohexyl ester, chloroformic acid-'y-chloropropyl ester, chloroformic acid phenyl ester or chloroformic acid 2,4-dimethylphenyl ester, chloroformic acid-4-chlorophenyl ester, as well as the corresponding bromine derivatives.

The reaction of the anthraquinone compounds of the Formula II with the halogeno formic acid esters of Formula III is preferably performed at low temperature (0- 50 C.) in the presence of acid-binding agents and, optionally, in inert organic solvents.

Suitable acid-binding agents are, in particular, tertiary nitrogen bases such as pyridine, picoline, quinoline, lepidine, aliphatic amines such as trimethylarnine and triethylamine, anilines such as N,N-dimethylaniline and N,N-diethylaniline, also alkali metal or alkaline-earth metal carbonate, hydrogen carbonates or hydroxides such as sodium hydrogen carbonate, potassium carbonate, barium carbonate, sodium hydroxide or barium hydroxide. Suitable inert organic solvents are optionally halogenated or nitrated aromatic hydrocarbons such as toluene, xylenes, chlorobenzene, dichlorobenzene or nitrobenzene as well as aliphatic halogenated hydrocarbons such as chloroform, carbon tetrachloride or tetrachloroethane, also lower aliphatic ketones such as acetone and cyclic others such as dioxane or tetrahydrofuran.

Preferred anthraquinone dyestufis of the Formula I, which are characterized by a good aflinity, by good levelling and buildup properties as well as by good fastness to sublimation and light on polyethylene glycol terephthalate fibres, correspond to the Formula VIII.

a III) wherein V represents the hydroxyl or amino group,

V represents the hydroxyl group or a phenylamino group, optionally ring-substituted by halogen such as chlorine, lower alkyl or lower alkoxy group,

X represents oxygen, sulphur, the -CONH- or --SO NH group, or also a Oalkylenegroup,

Y represents a lower alkylene group, and

R" represents a lower alkyl group or a phenyl radical, optionally substituted by halogen, such as chlorine, or a lower alkyl group such as a methyl group.

Further anthraquinone dyestuffs, according to the invention, which likewise are characterized by a good affinity and levelling property, as well as by good fastness to light of the polyester dyeings produced therewith, are those of the Formulae IX and X,

CHaO-CO O R" and R'-NH OH -(o-Y')1-2-0.oooR" wherein V V Y and R have the meaning given under Formula VIII, and R represents a lower alkyl group or preferably hydrogen.

In this specification, including the claims, the term lower applied to alkyl, alkylene and alkoxy groups or moieties means that such groups or moieties have at most 5 carbon atoms.

Anthraquinone dyestulfs of Formula I, wherein the ROOCOY grouping is linked to the anthraquinone nucleus by way of a -NHphenylene, NHphenylene--O or NHphenylene-S group may also be produced by condensing a fl-halogeno-anthraquinone compound of Formula XI,

wherein A" represents a B-anthraquinonyl radical which contains a hydroxyl group in the adjacent OL-POSltiOIl, and Hal represents chlorine or bromine, with an amino compound of Formula XII,

NH arylene YOCOOR (XII) wherein arylene represents a benzene nucleus, optionally substituted by halogen such as chlorine, or by lower alkyl groups, Q" represents the direct bond oxygen or sulphur and Y and R have the meaning given under Formula I,

whereby the starting materials are so chosen that the final dyestulf contains no-water-solubilizing groups dissociating acid in water.

B-Halogeno-anthraquinone compounds of Formula XI, usable according to the invention, are for the most part known. Examples of these are: 1-hydroxy-2-bromo-anthraquinone, 1,4-dihydroxy-Z-bromoanthraquinone and 1, 4-dihydroxy-Z-chloro-anthraquinone.

Amines of the Formula XII to be reacted with the latter compounds of the Formula XI can be produced in a known manner e.g. by reacting a nitro compound of the Formula XIII,

NO arylene- "--YOH (XIII) wherein arylene, Q" and Y have the meaning given R represents hydrogen or a lower alkyl group, n represents 1 or 2, and R and Y have the meaning given under Formula I, and

wherein the benzene ring B may be further substituted by halogen or lower alkyl groups, may be produced by condensing a disulfonated anthraquinone compound of Forrnula XV SOaH Hogs

HY n.1,

with a compound of Formula XVI (O--Y) n-o-o o o R (XVI) to a monosulfonated anthraquinone compound of Formula XVII and then splitting off the sulphonic acid group of this latter compound with a reducing agent, whereby the starting materials are so chosen that the final dyestulf contains no water-solubilizing groups dissociating acid in water.

A further process for the production of anthraquinone dyestuffs of the Formula XIV comprises oxidizing an anthraquinone compound of Formula XVIII,

I NH-R I I wherein R' represents hydrogen or a lower alkyl group, to the corresponding quinonimino compound, for example with manganese dioxide and then reacting the latter with a compound of the Formula XVI given above, whereby the starting materials are so chosen that the final dyestuft contains no water-solubilizing groups dissociating acid in water.

The new anthraquinone dyestuffs of the Formula -I are yellow to deeply colored, crystalline, diflicultly water-soluble substances. They can be obtained analytically pure by recrystallization from organic solvents, but such purification is generally not necessary for their use in dyeing.

They are suitable for the dyeing or printing of synthetic organic fibres, e.g. for the dyeing of textile fibres made from linear, high-molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols such as polyethylene glycol terephthalate or poly-(1,4-cyclohexanedimethylol-terephthalate) as well as for the dyeing of textile fibres made from cellulose-2-, -2/2-acetate or cellulose triacetate. These dyestutfs can, however, also be used for the dyeing of synthetic polyamide fibres such as polyhexamethylene adipamide, polycaprolactam or polyaminoundecanoic acid, as well as for the dyeing of polyolefins, especially polypropylene fibres, and also for the dyeing of polyamide in the mass.

Furthermore, they are suitable, depending on the composition, for the dyeing of lacquers, oils and waxes, as well as for the dyeing of cellulose derivatives, particularly cellulose esters such as cellulose acetate, in the mass.

Preferably, the dyeing of the mentioned fibre materials with the difiicultly water-soluble anthraquinone dyestuffs, according to the invention, is carried out from aqueous dispersion. It is therefore advantageous to finely divide the final materials of the Formula I, usable as dispersion dyestuffs, by grinding them with dispersion agents and possibly with further grinding auxiliaries.

Anionic dispersing agents suitable for the purpose are, e.g. the alkylaryl sulphonates, the condensation products of formaldehyde with naphthalene sulphonic acid, the lignin sulphonates; suitable non-ionogenic dispersing agents are, e.g. the fatty alcohol or alkylphenyl-polyglycol ethers with higher alkyl radical.

The dyeing of the polyester fibres with the difiicultly water-soluble dyestuifs, according to the invention, from aqueous dispersions, is carried out by the usual processes for polyester materials. Polyesters of aromatic polycarboxylic acids with polyvalent alcohols are preferably dyed at temperatures of above 100 C. under pressure. But the dyeing can also be performed at the boiling point of the dye bath in the presence of dye carriers, e.g. phenylphenols, polychlorobenzene compounds or similar auxiliaries, or by using the Thermosol process, i.e. pad-dye ing with a subsequent treatment in the heat, e.g. thermofixing at l902l0 C. Cellulose-Z-Vz-acetate fibres are preferably dyed at temperatures of 80-85 C., whereas cellulose triacetate fibres, as well as synthetic polyamide fibre material, are advantageously dyed at the boiling 8 point of the dye bath. The use of dye carriers is not necessary in the dyeing of cellu1ose2 /2-acetate or polyamide fibres. Anthraquinone dyestuffs, according to the invention, can also be used for the printing of the stated materials using normal methods.

The anthraquinone dyestuffs of the Formula I, usable as dispersion dyestuffs, draw on to the previously mentioned synthetic organic fibre material, especially on to polyethylene glycol terephthalate textile fibres, very well and they produce thereon strong' yellow, orange, red violet, blue and green dyeings which have very good fastness to light, washing, rubbing, perspiration, sublimation, solvents and decatizing. In this respect, mixtures of anthraquinone dyestuffs according to the invention behave particularly favorably.

Furthermore, anthraquinone dyestuffs, according to the invention, can also very well be used in admixture with other dispersion dyestuffs, which are fast to sublimation, for the dyeing of textile material using the pad-dyeing/ thermofixing process. Particularly worthy of note is the fact that dyestufls of the Formula I produce, in the dyeing of closely woven polyester fabrics or firmly twisted polyester yarns, even dyeings right through.

Moreover, the dyestuffs of the Formula I possess the valuable property of being able to produce on textured polyester fibres, e.g. Crimplene, very deep and nonstreaky dyeings which also have good fastness properties, particularly fastness to light and sublimation. The new anthraquinone dyestutfs also have good stability in the dye liquor and to boiling.

The following examples illustrate the invention. The temperatures are given in degrees centigrade.

EXAMPLE 1 29.9 g. of 1-amino-2-p-hydroxyethoxy-4-hydroxyanthraquinone are dissolved at 50 in 300 g. of pyridine and to the deep red solution are added dropwise, after rapid cooling of the solution of 0-10" and while the latter is being vigorously stirred, 31 g. of chloroformic acid phenyl ester. The reaction is complete after one hour at this temperature. The reaction product of the formula I OH precipitates, on stirring the solution with 300 g. of methanol at 20, in a crystalline form; it is filtered ofi, washed with methanol and dried.

Fibres made from cellulose diand triacetate, as well as from polyethylene terephthalate, are dyed in the aqueous dispersion of this finely divided dyestutf in very pure and even red shades. The dyeings have very good fastness to light, sublimation and rubbing.

If, instead of the 29.9 g. of l-amino-Z-B-hydroxyethoxy- 4-hydroxyanthraquinone, equivalent amounts of an anthraquinone compound listed in the following Table 1, column H, are used, and instead of the 31 g. of chloroformic acid phenyl ester, equivalent amounts of a halogen formic acid ester given in column III of the same table, using otherwise the same procedure as described in the example, then dyestuffs are obtained which dye polyethylene glycol terephthalate fibres in the shades listed in column IV of this table, these shades likewise having fastness to light and to sublimation.

TABLE 1 Shade on polyethylene glycol tera hthalate No; Anthraquinone aompound Halogen formic acid ester 11 res 2 0 NH Red.

|| cm 01000 -cm 0 CHzH-CHsOH 3.....-... OH (8 0H 010000111001: Orange.

A ocmcmon 4...; NH, clcoocmcl Red.

5 0 NH: CICOOCHI Bed.

0 CHzCHaOH 6"; -3 O NH. CICOOCHPCH=CHQ Red 0C CHaOH O l O H 7 2.--; 0 H: Bad.

I OH; 01-0 0 O CH:

0 CHa-CHzOH 8..;:.:. I: O OH Orange.

8 CHaCHzOH Y an 9 I IiIHa CH: Red.

CIC 0 O C O CHaCHaO CHaCHaOH I OH 10..-;22: I? 010 0 0 CzHl Red.

0 CHaCHaOH I II 0 OH 11- 581316 88 above- ClCOOCaHl Red. 12 fi ClCOOCIHI Bad. 1? fi CICOOCnHu Bed.

14 do Rad.

4 TABLE 1-Continued Shade on polyethylene glycol terephthalate Anthraquinone compound Halegen lormicacid ester fibres Same as Example 1'1 clcoocmcmm- Red.

(n) NH; C1COOCH3CH| Red.

0 CHzCHgO-Q-OCHaGHnOH 17 (I? NE, CICOOCH; Blue.

-SCH:C HzOH 8 -C H1O H: 0 H

l 0 NH: I

18 ('1') NH: GICOOCaHy Ruby red.

SCHzCHaCHaOH 19 0 EN1 Bad;

I C10 0 O- OCHzCHzCHaOCHzCHaCHaOH 20 Samoas abov CICOOCzH; 7 Red.

21 O NH; Red.

OCHsCHz-S-CHzCHaOH I O H 22 Sameasabov -5: 010000,;1. Red.

23.. (6 NH: ClCOOCzHs Red.

(1; ocmomocmcmon 24 Same as abov Red.

25 (ll) NH: Same as above Red.

as Sameasabov v 01000023. Red.

21 3 NH: cxcooogm v v 1m.

(OGHzCHaMOH I 0 NH 28 "S b0 Rd.

TABLE 1Continued Shade on polyethylene glycol tel-eph- Halogen formic thalate No Anthraqulnone compound acid ester fibres 29 |Ol IiIHg OlCOOCaHs Red.

OCHzCHnCHOH I AH 30 NH: ClCOOCaH; Ruby red.

A somomoomomon EXAMPLE 31 acid isopropyl ester. Stirring afterwards proceeds for a 40.6 g. of l,5-dihydroxy-4,8-diamino-2-(4'-fi-hydroxyethoxy)-phenylanthraquinone are homogeneously mixed by stirring in 400 g. of N,N-dimethylaniline and to the mixture are added at 5-10", 16.3 g. of chloroformic acid ethyl ester within half an hour. After a further hour at this temperature, the reaction mixture is diluted with 200 g. of ethanol, whereupon, the dyestufi of the formula OH OCHzCIhOCOOCaHt OH NH:

7 g. of potassium carbonate and 34.5 g. of 1-amino-4- hydroxy-2-p,'y dihydroxypropylmercaptoanthraquinone are homogeneously mixed by stirring in 380 g. of chlorobenzene and to the mixture are added, at 0-10 and in the course of 45 minutes, 24.5 g. of chloroformic fl) NH: @A

OH CH:

precipitates as black-violet powder. It is filtered off, washed with pertroleum ether and with water and dried.

The aqueous dispersion of the finely divided dyestutf dyes cellulose diand triacetate fibres as well as, in particular, polyethylene glycol terephthalate fibres, in fll, even, bluish-red shades. The dyeings have good fastness to light, rubbing and wet processing.

The same dyestuff is obtained by using in the above example, instead of the 24.5 g. of chloroformic acid isopropyl ester, 33.4 g. of bromoformic acid isopropyl ester, using otherwise the same procedure as prescribed above.

If, instead of the 34.5 g. of 1-amino-4-hydroxy-2- B,'y-dihydroxypropylmercaptoanthraquinone, equivalent amounts of an anthraquinone compound listed in the following Table 2, column II, are used, and instead of the 24.5 g. of chloroformic acid isopropyl ester, equivalent amounts of a halogen formic acid ester given in column III of the same table, using otherwise the same procedure as described in the example, then dyestuffs are obtained which dye polyethylene glycol terephthalate fibres in the shades listed in column IV of this table, these shades likewise having fastness to light and to sublimation.

TABLE 2 Shade on polyethyl ene glycol ter I ephthalate No. Anthraqumone compound Halogen formic acid ester fibres 33 NH: /OH; Bluish red.

A 010 O 0 C H S-CH2C Hz-OH ll l O OH 34 0 NH: D0.

II 010 O 0- S- 0 Hz C H: O H

I] l 0 OH TABLE 2-Continued Shade on polyethylene glycol tereph- Halogen formic thalate N0, Anthraquinone compound acid ester fibres as Same as Example 34 010 0 0H. Bluishflred. as ..do 010 00 CHZGHI Do. 37 fln ClCOOClH. D0.

39. (I) NHa C1--COO CaH; Do;

s-omr Jn-on-cmon 40""; Same as above Q Do;

EXAMPLE 41 2 o NHa To a mixture of 350 g. of chlorobenzene and 80 g. of H CO triethylamine are added 35.1 g. of l,4-diaminoanthra quinone 2 3-dicarboxylic acid-fi-hydroxyethylimide and homogeneously mixed by stirring at 40. The suspension N Cmomo CHzCH O 0 is cooled to 010 and 19 g. of chloroformic acid methyl C0 ester are added dropwise in the course of half an hour. i g To complete the reaction, stirring is carried out for a further hour at this temperature. 200 g. of methanol are then 0 NH added, whereupon the corresponding dyestufi of the 1 C0 formula A 02H /N--t1HCHaCHs-OCOO 0 Y 1 00 5H: 0 NH! NH C N-omornocooom ii Co Y H3 H- H 0-0 0-0 i NH. J 4.5 C G precipitates in a finely divided form from the reaction 0 NH: mixture. The dyestufi is filtered off, washed with metha- A C0 1101 and dried.

Fabrics made from polyethylene glycol terephthalate MCHOHZCHVowmcmcgrmc04,653 fibres are dyed from the aqueous dispersion of the finely divided dyestuif in very pure, even, turquoise blue shades. C0 The'dyeings have good fastness to light and to rubbing. l, NH2

If, the above example, instead of 19 g. of chloroformic acid methylester, 26.3 g. of chloroformic acid n-butylester 0 NH: or 21.7 g. of chloroformic acid ethylester are used, then H CO two further dyestufis are obtained which produce turquoise bluedyeings on polyethylene glycol terephthalate fibres. A very similar dyestufi is also obtained by using instead of the 35.1 g. of 1,4-diaminoanthraquinone-2,3- c dicarboxylic acid p-hydroxyethylimide, 36.5 g. of 1,4- 3 i l diamino-anthraquinone 2,3-dicarboxylic acid-* -hydroxypropylirnide, and otherwise acylating as in the above example. A somewhat less greenish blue dyestuif is obtained by replacing, in the above example, the 35.1 g. EXAMPLE 42 of 1,4-diamino-anthraquinone-2,3-dicarboxylic acid-B-hy- 34.4 of 1 amino 2 hydrxymethy1 4 phenylamino droxyethylimlde by 35 of l'aflunozp'hydroxyethyl'3' 7g anthraquinone are dissolved, while heat is being applied,

oxo 4,7 diamino 5,6 phthaloyl-dihydroisoindole, proceeding otherwise according to the above example.

In an analogous way the dyestuffs listed below were obtained. They dyed polyester fibers in turquoise blue shades.

in 300 g. of pyridine. The deep blue solution is cooled to 0-5 and to this are added dropwise at this temperature, while the solution is being well stirred, 28 g. of chloroformic acid amyl ester. After the dropwise addition is completed, the reaction mixture is stirred for a further 3 17 hours at 0-10 to complete the acylation. To effect precipitation of the dyestufi of the formula 200 g. of methanol are then added to the reaction mixture.

anol and dried.

The finely divided dyestuff evenly dyes fibres made from cellulose diand triacetate, as well as polyethylene glycol terephthalate fibres, in aqueous dispersion, in deep blue, shades having good fastness to light and to sublimation.

By using, instead of the 34.4 g. of 1-amino-2-hydroxymethyl-4-phenylaminoanthraquinone, equivalent amounts of an anthraquinone compound given in the following Table 3, column H, and instead of the 28 g. of chloroformic acid-n-amyl ester, equivalent amounts of a halogen formic acid ester given in column III of the same table, with otherwise the same procedure as stated in the example, dyestuifs are obtained which dye polyethylene glycol terephthalate fibres in the shades listed in column IV of this table, these shades likewise having fastness to light and sublimation.

TABLE 3 Shade on polyethylene glycol tereph- N0. Anthraquinone compound Halogen formic acid ester thalate fibres Bed. 01000- CH:

44...:::: 0 NH: /CH| Reddlsh blue;

CIC 0 O CH CHQOH CHzCl I O NH 45...::: O NH; ClCOOCHaCHaCHaCl Red:

CHzOH 46 O NH: CICOOCHsGHzB! Reds o-Qc mon l O H 47...: O NH, BlCOOCaHs Blue Violet;

TABLE 3-Continued Shade on polyethylene glycol tereph- No. Anthraquinone compound Halogen formic acid ester thalate fibres 50- (I) NH; CIOOOCH; Blue.

I O NH 51 Same Q5 abovenfle C1-COOCsH D- 62 fin C'ICOOCHHKH) D0.

53 (In D0.

54 (3 NH: Gl-CO0-0H Red-violet.-

s-Q-cmon $5 precipitates, upon the addition of 400 g. of methanol,

CHaCHsO C 0 O CIH] in crystalline form; the dyestufi is filtered off, washed with methanol and dried.

The finely divided dyestufi very evenly dyes, in aqueous dispersion, fabrics made from polyethylene glycol terephthalate fibres in deep blue shades having very good fastness to rubbing and to sublimation.

By using, instead of 39 g. of l-amino-Z-fl-hydroxyethylmercapto 4 anilinoanthraquinone, equivalent amounts of an anthraquinone compound given in the following Table 4, column H, and instead of 16.3 g. of chloroformic acid ethyl ester, halogen formic acid ester, using otherwise the same procedure as described in the example, dyestufis are obtained which dye polyethylene glycol terephthalate fibres in the shades listed in column IV of this table. 7

TABLE 4 Y Y 20 glycol er- Halogen formic acid shthalete No. Anthraquinone compound ester bras ii? IilH CICOOCH CHCh Blue.

S C1110 HaOE CH] 6 I'm 4:11.

57...: O NH; ClOOOCgH Do.

S CHfl'JHCHIOH o (a N H; C1CO0C:H Cl ii-0 0 GHICHQOH I 0 NH CH| TABLE 4- Continued Shade on polyethylone glycol tereph- Halogen formic acid thalate No Anthraqulnone compound ester fibres 59. (N) NE; 010000 1111 Violet-blue.

O CHQCHHOH g mac-Q0 0H.

60. 0 NH, Blue.

II OH 010 O O- S CHzHCHlOH CH] 8 NHCE 61...; NH: Cl-C00-CzH| Do.

ms -0 mcmon 62...-.- (1.) NH: C1-C00C|H Violet-blue.-

O-GHaCHaOH Q NH 63...: El) NH: 01000011; Blue:

ms cmcmon 64 Same Bsabove CICOOC H; Do: 65 -do- ClCOOC Hp(n) D0.

66.-.. 0 NH; Do.

I! I OH 010 O 0- S CHaHCHIOH 67... (I? NH; Samo as above. Do:

68.-... 0 NH; CICOOCzH; Do:

I! OH S OHZJJHCHZOH TABLE 4Continued Shade on polyethylene glycol tereph- Halogen formic thalate No. Anthraqulnone compound acid ester fibres 69..." NH, (ll-COOCzH; Blue.

OCHaCHzOH Cl-GOO-C H; Violet-blue.

EXAMPLE 71 @QoQ-eomnomomocoommm gradually precipitates in a fine-crystalline form. The reaction product is filtered off, washed on the filter with ethyl alcohol and afterwards dried.

The finely divided dyestuif dyes polyethylene glycol terephthalate fibres, in aqueous dispersion, in brilliant red shades having very good fastness to light, sublimation and rubbing.

By using, instead of the 45.4 g. of l-amino-4-hydroxyanthraquinone-2-phenoxy-4-sulphonic acid fi hydroxyethylamide, equivalent amounts of an anthraquinone compound given in the following Table 5, column 11, and instead of the 33 g. of chloroformic acid-,B-bromoethyl ester, equivalent amounts of a halogen formic acid ester, given in column 111 of the same table, with otherwise the same procedure as described in the example, dyestulfs are obtained which dye polyethylene glycol terephthalate fibres in the shades listed in column IV of this table, these shades likewise having fastness to light and sublimation.

TABLE 5 Shade on polyethylene Halogen formic glfiiiaii N0; Anthraqulnone oompoimd acid ester fibres 72 Ill) NH CICOOCHI Red violet:

o-Q-somuomomou "urea-7.: O NH: Ci-OOO CgHrBl' Do:

i O -SO:NHCH:CH;OH

o-Q-somuomomon NH 74..=.-::== NH: 01-00005)! Do;

o-Qomncmcmomou NHI TABLE 5Continued Shade on polyethylene glycol terv Halogen formic. ephthelate No. Anthraqulnone compound acid ester fibres 75 O N H: C1000 01H Ruby red.

s-Qomncmoncmon 76 (1) NH: (ll-COOCzH D0.

s-Q-somncm-cmomon 77 O NH: CICOOC|H| Red.

oQsomrrcmcmorr B B0 Red. 78 me as e vs (Coo Q 79 do ClCOOCtHQ Orange.

80 O NH: CICOO 01H; Ruby red.

ll Q? s-Qsonmcmomon EXAMPLE 81 EXAMPLE 82 39.1 g. l-amino 4 hydroxy-Z-(4'-fi-hydroxyethoxyphenoxy)-anthraquinone are sprinkled into 350 m1. of pyridine at -40 whilst the mixture is being vigorously stirred. The mixture is cooled to 10-15 and to it are added, in small portions, 43.3 g. of chloroformic acid tribrornoethyl ester. Stirring is maintained at this temperature until the starting material can no longer be detected by thin-layer chromatography.

With the addition of 350 ml. of methanol, the formed dyestufl of the formula NE, o-Q-o omomocooonzcnn To a solution of 31.2 g. of l-aminoanthraquinone-Z- carboxylic acid-'y-hydroxypropylamide in 300 ml. of pyridine are added in small portions at 040, whilst the solution is being vigorously stirred, 46.6 g. of chloroformic acid-p-methylphenyl ester within one hour. To complete the reaction, the reaction mixture is held at this temperature for a further two hours. By the slow dropwise addition of 50 ml. of water, the dyestuif of the formula is precipitated as fine red powder. The dyestulf is filtered off, washed with water until the reaction is neutral and with a little methanol, and then dried.

From aqueous dispersion, the finely divided dyestufi dyes fibres made from cellulose diand triacetate, as well as, in particular, fibres made from polyethylene terephthalate, in very even red shades having good fastness to light and to rubbing. 1

By using, instead of the 31.2 g. of 1-aminoanthraquinone-Z-carboxylic acid-y-hydroxypropylamide, equivalent amounts of an anthraquinone compound given in the following Table 6, column II, and instead of the 46.6 g. of chloroformic acid p methoxyphenyl ester, equivalent amounts of a halogen formic acid ester given in column III of the same table, with otherwise the same procedure as given in the example, dyestuflis are obtained which 2.7 dye polyethylene glycol terephthalate fibres in the shades listed in column IV of this table, these shades likewisc having fasness to light and to sublimation.

TABLE 6 V v t H Shade on polyethylene glycol terophthalate No. Anthraqulnono compound Halogen formic acid ester fibres 83..... 0 N E; Rod.

, ClCOO CONHCHaCHaCHaOH 84...: 0 NH, CH; Blue;

010 0 0 CH CONHCHzCHaOH CHI CICOOCHKn) Do.-

S OzNHCHaCHaOH C ONHCHaCHzOH 87.--..- o N 01000011 Blue;

H: I 0H oonncmrkcmon cm NHCE cm 88.-.: 0 NH| 01000013 REG- WCONHCHaCHaOH 89...; O NH: CXC O 0 02K; Green.

mcoocmcmon 0 NH 01600013; Yellowlsh green;

S 010 CH3CH20E o N B a.-

Cl-COOQ e C OOCHsCH1OH TABLE ti-Continued Shade on polyethylene glycol terephthalate No. Anthraquinone compound Halogen formic acid ester fibres 92- (I? NH, 010 0 04H. Bluelsh red.

C 0 O CHzOHrOH H 0 NH: 93-..; ClCOOC H; Blue;

G oooomomon Y Q 94.-.: O NH: CIC 0 0 04B. Red.-

@ solo omomon 95...: NH; OlC 0 0 C2H Blue.-

@ cooomomo omomon Q 95...: 0 NH; 010 0 O C4H| D0;

0 0 0 CHiCEOH NHQ EXAMPLE 97 42.3 g. of l-hydroxy 2 a hydroxyethylsulphonyl-4- phenylaminoanthraquinone are homogeneously mixed by stirring at room temperature in 350 m1. of pyridine. After slight cooling of this mixture to -15, 34 g. of chloroformic acid butyl ester are added to it dropwise within minutes. The mixture is maintained at this temperature until the starting material is no longer detectable. 'Ihe dyestufli of the formula o on A SOzCHzCHzOCOOCtHr ii I O NH- obtained by using, instead of the 42.3 g. of l-hydroxy-Z- fi-hydroxyethylsulphonyl 4 phenylaminoanthraquinone, 42.2 g. of 1-amino-2-p-hydroxyethylsulphonyl-4-phenylaminoanthraquinone, proceeding otherwise according to the above example.

' EXAMPLE 98 31.9 g. of 1,4-dihydroxy-Z-bromoanthraquinone and 56 g. of 4'-(p-ethoxycarbonyloxy-ethoxy)-aniline are stirred up in 350 g. of boiling ethylene glycol monomethyl ether for 15 hours; to the deep violet-red reaction solution are added, at 100, 70 ml. of water and the solution is cooled to room temperature. The precipitated crystalline dyestufi of the formula on Y I O ONE-Q-O-CIIzCHz-O-COOCzH:

is then filtered olf, washed with methanol and dried.

From an aqueous dispersion, the finely-divided dyestufi dyes fabric, made from polyethylene terephthalate fibres, in even red-violet shades having excellent fastness to light and to sublimation.

By using, instead of the 31.9 g. of 1,4-dihydroxy-2- bromoanthraquinone, equivalent amounts of an anthraquinone compound, given in the following Table 7, column II, and instead of the 56 g. of 4'-(B-ethoxy-carbon- 3'1 yloxy-ethoxy)-aniline, equivalent amounts of an aniline derivative given in column 11 of the same table, with otherwise the same procedure as described in the example, dyestufis are obtained which dye polyethylene glycol terephthalate fibres in the shades" listed in column IV of this table, these shades likewise having fastness to light and to sublimation.

very good fastncss to sublimation, are obtained on polyethylene terephthalate fibres 'by replacing, in the above example, the 30.4 g. of l(N),9-(2'-methyl)-pyridino-2- fl-hydroxyethylaminoanthraquinone by 32.3 g. of 1(N),9- (N)-pyrimidino-2-fi-hydroxyethylthio 4 aminoanthraquinone and acylating by using either the same amount of chloroformic acid phenyl ester or by using 21.7 g. of

TABLE 1 Shade on polyethylene glycol terephthalate No. Anthraquinone compound Halogen formic acid ester fibres 99 0 on Red.

NH OCHaCHaOCOOCH:

100 on Red.

NH -CH3CH20COOCIHI 101 0 OH OH Bed.

B Nm-Qoomoncmooocirn 102 Same as above Red.

NH 00H=oH=0-coo 01 s fi Red.

NH QCHICHzO-COOOIHI 104 Red.

rvnQroomomnocoomm 105 do Red. NH r mocoomm 106 .do.. Red.

NH cmomcmocooofia EXAMPLE 107 chloroformic acid ethyl ester, under otherwise the same 30.4 g. of l (N) ,9- (2'-methyl)-pyridino-2-p-hydroxy ethylaminoanth'raquinone are homogeneously mixed in 300 g. of 3-piooline at 0-5"; and at the same temperature are then added dropwise, within one hour, 31 g. of chloroformic acid phenyl ester. After 4 hours, the reaction product of the formula mrcmom-o-coo-Q conditions.

EXAMPLE 108 To a solution of 800 g. of 96% sulphuric acid and 22 g. of o-boric acid are added, at 4050 and within A hour, 48 g. of l,5-dihydroxy-4,8-diaminoanthraquinone- 3,6-disulphonic acid. The solution is cooled to 10 and to it are then added 38 g. of fl-monophenoxy-diethyl carbonate. Stirring is maintained for half an hour at 10 and the temperature then allowed to rise within half an hour to room temperature. After this period of time, the reaction mixture is poured on to two litres of ice/methanol (30% methanol) and then heated for 4 hours to 60.

The product of the formula NH: o on A -0 CHzCHzOCOOCzHi 1 I H O NH:

is filtered ofl, washed with 5% brine and dried.

33 g. of the dried product are suspended in 400 m1. of

50% methanol, to the suspension are added 40 ml. of

33 concentrated ammonia and to the whole are added dropwise 18 g. of sodium hyposulphite in 60 ml. water, the mixture being then heated for one hour to 40-50.

The dyestuif of the formula NH: (I?

AUG-OCHzCl-LO 00cm H A l lHz precipitats out, is washed first with cold water, then with hot water and finally with hot methanol, and dried. The dyestuff is identical to that obtained according to Example 31.

EXAMPLE 109 28.6 g. of 1,5-dihydroxy-4,8-diaminoanthraquinone are added to 270 ml. of 95% sulphuric acid at 20-30 within 25 minutes. The yellowish brown solution is cooled to 05 and oxidized with 18 g. of manganese dioxide, with in 30 minutes, to the corresponding quinonimine. The deep-blue solution of the quinonimine is filtered through a glass frit, the residue washed with 180 ml. of 96% sulphuric acid, cooled to 30 and 30.5 g. of fl-monophenoxy-diethyl carbonate are added. The reaction at this precipitates out in crystalline form as the solution is stirred with ice. The reaction product is filtered 01f,

. washed neutral with water, subsequently treated with methanol and dried.

This dyestuff is identical to that stated under Example 31.

If, instead of the 28.6 g. of 1,5-dihydroxy-4,8-diaminoanthraquinone equivalent amounts of the anthraquinone compound given in the following Table '8, column II, are used, or if the 30.5 g. of B-monophenoxydiethyl carbonate are replaced with equivalent amounts of the phenoxy compound given in column III of the same table, with otherwise the same procedure as described in the Example 109', then dyestuffs are obtained which dye polyethylene glycol terephthalate fibres in shades having similar properties, these shades being listed in column IV of the same table.

TABLE 8 Shade on polyethylene glycol terephthalate N o. Anthraquinone compound Halogen formic acid ester fibres 110 NH2 0 0H Blue.

A H H- OOHzCHzOCOOCHz H 0 11TH:

111 Same as above /CH; Do.

3G0 CHz0-H:0C 0 0 on 112 (in D0.

HQ-O cmomo-o o oolru-n 113 do Do;

HQO cmom-o-o o o CzHr-n 114 do CH3 D0.

HO CHzOHz-O-C o o-om-o 115 do CH3 D0.

HQ-O c1120 112-0-0 0 0-05 CzHg 116 do D0.

nQ-o CHzCHr-O-C 0 0G 117 do Do.

H -0 OH:CH2O--COO 118 do Do.

H ocmcm-o-oooQm 119 do Do.

HQ-O cmcm-o-o 0 o 120 (in D0.

TABLE 8-Contlnued Shade on polyethylene glycol terephthalate No. Anthraqulnone compound Halogen formic acid ester fibres 121 S as E m lo 120 Blue.

- we m p HOCHz-([3HCH:-0-G 001B 22 D0. 1 do n--oomorn-o-omon=o-o o o 02H:

123 do D0.

H-Q-oomomomoomomcmooooczn,

124 do 7 Do.

H OCHzCHzO CHzCHzCHgO-COOCzHI 125 do D0.

H OCHaCHzCHgOCHnCHzO-COOCzE 126 do D0.

H OCHzCHgO O OO CHnGHzBr H 0 H D0. 127 c 0 H- o cmomo-o 0 o 02H:

l H O DIE-C 128-.-.-..:..-. CaHiNH f) 0H Same as above Do.

H O NHCaH EXAMPLE 12.9 100 g. of fabric made from polyethylene glycol tere- 28.6 g. of 1,5-dihydroxy-4,8-diaminoanthraquinone are introduced in small portions within half an hour at into 270 ml. of 96% sulphuric acid, whereupon the yellowish-brown solution is cooled to 0 and, within a fur ther half hour, oxidized with 18 g. of manganese dioxide to quinonimine. The obtained deep blue solution is clarified through a glass frit and to the solution are added, at -10 to 5, 31 g. of 'B-(p-methylphenoxy) -ethyl-methyl carbonate. At this temperature the reaction is completed after one hour, the formed reaction product of the formula NH: O OH CH; II I EXAMPLE 1 3 0 In a pressure dyeing apparatus, 2 g. of the dyestuff, obtained according to Example 31, are finely suspended in 2000 g. of water containing 4 g. of oleylpolyglycol ether. The pH-value of the dye bath is adjusted with acetic acid to 4-5.

phthalate are then introduced at 50, the dye bath is heated within 30 minutes to 140 and dyeing is carried out at this temperature for 50 minutes. The dyeing is afterwards rinsed with water, soaped and dried. Under these conditions is obtained a deeply colored, level, blue dyeing having fastness to perspiration, light and sublimation.

The dyestufl described in the other examples produce, using this process, dyeings of equal quality.

EXAMPLE 13 l Polyethylene glycol terephthalate fabric is impregnated on a padding machine at 40 with a dye liquor of the following composition:

20 g. of the dyestufi', obtained according to Example 32,

finely dispersed in 7 .5 g. of sodium alginate,

20 g. of triethanolaminc,

20 g. of octylphenolpolyglycol ether, and

900 g. of water.

The fabric, squeezed out to ca. is dried at 100 and after-wards fixed during 30 seconds at a temperature of 210. The dyed material is rinsed with water, soaped and dried. Under these conditions is obtained a deeply colored blueish-red dyeing having fastness to rubbing, light and sublimation.

The dyestuifs described in the other examples produce, with application of this process, dyeings of equal quality.

EXAMPLE 132 A mixture consisting of 1 g. of the dyestufi obtained according to Example 1 and l g. of the dyestufl", obtained according to Example 10, are dispersed in 4000 g. of water. To this dispersion are added, as swelling agent, 12 g. of the sodium salt of o-phenylphenol, as well as 12 g.

of diammonium phosphate, and 100 g. of yarn made from polyethylene glycol terephthalate are dyed for 1% hours at 9598. The dyeing is rinsed and afterwards treated with aqueous sodium hydroxide solution and a dispersing agent.

In this manner is obtained a deeply colored red dyeing having fastness to light and to sublimation.

By replacing, in the above example, the 100 g. of polyethylene glycol terephthalate yam by 100 g. of cellulose triacetic fabric, dyeing under the given conditions and subsequently rinsing with water, a deeply colored red dyeing is obtained having very good fastness to washing and to sublimation.

What is claimed is:

1. An anthraquinone dyestufi of the formula wherein R is C -C -a1kyl, cyclohexyl, phenyl or phenyl optionally substituted by one or two substituents selected 0 NH: O N-CHzCHzO-OOOCiHg Y I C O 4. An anthraquinone dyestufi according to claim 1 wherein the alkylene group contains at most 4 carbons, and the phenyl group is substituted by one or two substituents selected from methyl, chlorine, or methoxy.

References Cited UNITED STATES PATENTS 3,668,219 6/1972 Otsuka et a1. 260-325 JOSEPH A. NARCAVAGE, Primary Examiner US. Cl. X.R. 

